Electrodialysis unit for water treatment

ABSTRACT

An electrodialysis unit comprises a plurality of cathodes, a plurality of anodes and a plurality of membranes; the cathodes and anodes being arranged alternately in an electrode stack, with membranes in between each cathode and anode, anode flow paths formed between the membranes and anodes and cathode flow paths formed between the membranes and cathodes; the electrodialysis unit further comprising: an inlet manifold for distributing water to the anode flow paths or to the cathode flow paths, wherein the inlet manifold comprises a first tube provided with holes along its length, the holes being connected to the flow paths, and a second tube located within and enclosed by the first tube, the second tube having an inlet at one end and being closed at its second end and the second tube being provided with holes along its length that open into the first tube.

The present invention relates to the treatment of water byelectrodialysis, such as a treatment in order to kill micro-organisms,preferably treatment of sea water such as ballast water treatment.

Ballast water is water transported by ships in the ballast water tanksor sometimes in other suitable spaces such as in cargo holds or in cargotanks. It is pumped into the tanks at a water “donor” location tocompensate for the changing of point of gravity as cargo and/or fuel isdischarged/consumed and hence to maintain stability. Correct ballastingis essential from a structural point of view and also used forperformance reasons in order to ensure proper propeller and rudderimmersion, proper bridge view as well as maintaining desired vesselmovement and handling characteristics. The ballast water is transportedto a water “recipient” location, generally at a point where the vesselis to be loaded with cargo, which is potentially outside thebio-geographic region of that of the ballast water origin. It may thenbe discharged as cargo is taken onboard. Ballast water may host a rangeof species including zooplankton, phytoplankton, bacteria and viruses.These may not have natural predators at the point of discharge and mayestablish and reproduce at the new location causing significant problemsfor the environment, industry and human health.

It is desirable to treat water and particularly ballast water in orderto kill or disable micro-organisms and to reduce or remove otherpollutants.

WO 2008/047084 describes a method and apparatus for ballast watertreatment including the use of electrodialysis in a membrane cell.Electrodialysis of this type is a fluid treatment process based onion-separation by applying an electric potential difference, eitherconstant or in pulses, between two electrodes separated by anion-exchange membrane. One electrode will perform as an anode (positivecharge) attracting negatively charged ions whilst the other will performas a cathode (negative charge) attracting positive charged ions. Thefluid in the compartment between the membrane and the anode will becomecharacterised by negatively charged ions with an excess of electrons andmay be referred to as the concentrate while the fluid in the compartmentbetween the membrane and the cathode will be characterised by thepresence of positive ions with a shortage of electrons and may bereferred to as the diluate.

In some electrodialysis processes, multiple membrane cells are arrangedinto a configuration called an electrodialysis stack, with alternatinganion and cation exchange membranes forming the multiple membrane cells,generally between a single anode and cathode. Known uses ofelectrodialysis are large scale brackish and seawater desalination andsalt production, and small and medium scale drinking water production.Electrodialysis is also used in the process industry for separation ofcertain contaminants such as heavy metals.

In the disclosure of WO 2008/047084 ballast water is treated byseparating a part of the ballast water from the main flow, passing itthrough the membrane cell, and returning a product of the membrane cellto the main flow. The returned product is mainly concentrate and thishas the effect of disabling or killing micro-organisms in the water. Theconcept of directing only a part of the water through theelectrodialysis treatment unit and returning a product of the membranecell to the water represented an advance in the art, since an effectivewater treatment is achieved without the need to pass the entire waterflow through the electrodialysis treatment unit.

Thus, the electrodialysis device of WO 2008/047084 provides anadvantageous form of electrodialysis treatment for use with watertreatments such as ballast water treatment. However, further work inrelation to the use of an electrodialysis treatment of this type totreat seawater such as ballast water has identified areas whereimprovements may be made.

The claims of this application relate to the seventh to ninth aspectsbelow. The other aspects set out below are not presently claimed hereinand are included to explain other related inventions.

Viewed from a first aspect, the present invention provides anelectrodialysis unit comprising: a cathode, an anode, a membrane betweenthe cathode and the anode, a cathode flow path for water flow along themembrane on the cathode side, an anode flow path for water flow alongthe membrane on the anode side, and a reaction zone formed between themembrane and the cathode where the cathode faces the anode, wherein thecathode flow path is arranged for laminar flow in the reaction zone andwherein the electrodialysis unit comprises flow conditioning elementsarranged to promote laminar flow in the incoming water flow to thecathode flow path.

Sea water is not purely a solution of water with sodium chloride butinstead includes other salts and compounds that result in secondaryreactions in addition to the well known sodium chloride and waterreactions. For example, magnesium salts can form about 3-4% of the saltsin sea water. One of the secondary reactions has been found to producebrucite, Mg(OH)₂, on the cathode side of the electrodialysis unit.Brucite has the appearance of a milky white sticky substance.Unexpectedly, the inventors have found that when normal seawater is usedthe electrodialysis process forms this brucite substance in theelectrodialysis unit and that brucite deposits build up in internal flowchannels. This problem is not disclosed in the known prior art. Theelectrodialysis unit of this aspect includes features to address thisnew problem.

Typically, conventional electrodialysis units will seek to promoteturbulence and secondary flows, since this mixing process is thought toaid the electrodialysis reactions and accelerate ion transport acrossthe membrane. Hence, conventionally laminar flow is not used and nomeasures are taken in the known devices to ensure laminar flow on thecathode side. The present arrangement is based on the realisation thatbrucite deposits are a potential problem and that by includingstructures to promote laminar flow the build-up of brucite can beavoided. The formation of brucite deposits is aided by turbulence anduneven or secondary flows in conventional electrodialysis units. Withthese flow patterns dead spots or zones of recirculating water flowform, where the brucite becomes trapped. This allows the brucite toagglomerate or coagulate and build into larger deposits.

Secondary flow structures do not occur if the flow is laminar. Byincorporating features intended to promote laminar flow before the waterenters the reaction zone the electrodialysis unit of this aspect reducesthe opportunity for agglomeration or coagulation of brucite and othercontaminants that may be formed in the reaction zone. Maintaining thelaminar flow through the reaction zone reduces the opportunity forcontaminants to become trapped or stuck within the device. The reactionzone is the region of the electrodialysis unit where the anode andcathode overlap sufficiently for the electrodialysis reaction to occur.When the formation of brucite deposits is avoided the unit requires lessfrequent cleaning. The build-up of other contaminants can also bereduced.

Preferably, the flow conditioning elements are arranged to promotelaminar flow in an area preceding the reaction zone. The cathode flowpath in the reaction zone may be a straight-sided flow path of generallyconstant dimensions. Areas in the flow path of varying shape and sizeare preferably outside of the reaction zone, and preferably spaced awayfrom the reaction zone.

Preferably the cathode flow path is free from obstructions in thereaction zone. This avoids the generation of turbulence, which wouldotherwise occur when water flows about an obstruction. Generally, anelectrodialysis unit will incorporate spacer elements to maintain adesired spacing between the membrane and the electrodes. In the priorart, these spaces are present on both the anode side and the cathodeside to keep the membrane in position. Preferably the electrodialysisunit of this aspect has no spacer element on the cathode side, i.e.spacer elements may be included only on the anode side of theion-exchange membrane. This avoids any obstruction from spacer elementson the cathode side and hence reduces turbulence on the cathode side.Since the brucite reaction does not occur on the anode side no problemarises from the presence of a spacer element generating turbulence inthe anode flow path.

In a preferred embodiment the unit is arranged such that there is agreater flow rate through the cathode flow path than through the anodeflow path. This is in order to provide a higher pressure on the cathodeside of the membrane. Hence, preferably there is a greater flow velocitythrough the cathode flow path than through the anode flow path. The flowvolume through the cathode flow path may also be larger than the flowvolume through the anode flow path. The higher pressure through thecathode flow path acts to push the membrane away from the cathode, whichcan reduce the opportunity for build-up of brucite deposits on themembrane. Moreover, the use of a higher flow rate, especially incombination with the laminar flow of this aspect, acts to wash away anybrucite deposits that may occur. A water inlet for the cathode flowpath(s) may be larger than a water inlet for the anode flow path(s). Ifwater is supplied at the same pressure to both inlets then this wouldresult the required increased flow rate and the flow velocity and flowvolume would both be higher if the cathode flow path(s) has the samecross-sectional area as the anode flow path(s).

The electrodialysis unit may include flow conditioning elements prior tothe reaction zone to promote even distribution of incoming water acrossthe widths of the cathode flow path and/or anode flow path. In thepreferred embodiment the cathode and anode flow paths are formed betweenplate shaped electrodes and hence will have an elongate slot shapedcross-section. A narrow slot shaped cross-section for the flow path canpromote laminar flow. For example, the cross-sections of the flow pathsmay be slots with a width of between 1 mm and 4 mm, preferably a widthof about 2 mm between the electrode and the membrane. The cross-sectionsof the cathode flow path and the anode flow path may be slots having thesame width. Flow conditioning elements used to ensure an evendistribution of incoming water across the width of a slot shapedcross-section will promote laminar flow.

The flow conditioning elements may comprise channels, baffles and/orguide vanes for even distribution of flow from one or more water inletpassages to the anode/cathode flow path. The incoming water flow ispreferably divided evenly across the width of the anode/cathode flowpath. In a particularly preferred embodiment the flow conditioningelements comprise flow channels extending in a fan shape from an inletpassage to the cathode/anode flow path.

The preferred embodiment utilises multiple repeated cathode and anodeplates arranged in layers in an electrode stack, with membranes inbetween each cathode and anode. This enables multiple electrodialysischambers to be formed in parallel, each with their own electrodes, andthis increases the rate at which water can be treated. Preferably, theelectrodialysis unit comprises a repetition of the sequence cathodeplate, membrane, anode plate, membrane, such that both sides of eachelectrode plate are utilised (aside from electrodes at the outer ends ofthe repeated sequence). Thus, each cathode plate in the central portionof the electrode stack would have a cathode flow path on each side ofthe plate. Similarly each anode plate would have an anode flow path oneach side.

In order to reduce disruption as the water flows into the electrode flowpaths after the flow conditioning elements, the leading edge of thecathode and/or anode preferably comprises a shaped end with increasingwidth. The shaped end may for example include a wedge shape and/orcurved portion. After the shaped end, the cathode/anode preferably takesthe form of a plate with constant width. A preferred shape for theshaped end is a symmetrical wedge shape with a rounded point. The use ofa shaped end acts to gently divide the flow along either side of theelectrode. Where the electrodialysis unit comprises spacer elements inthe anode flow path these spacer elements are preferably located afterthe shaped end.

The shaped end of the cathode and/or anode may be formed by shaping theelectrode material, e.g. by machining. Alternatively, the shaped end maybe formed by the addition of a shaped component formed of a differentmaterial. This is advantageous when the electrode material is difficultand/or costly to shape. For example, if a titanium electrode is used.The shaped end may be a moulded plastic insert.

Preferably the electrodialysis unit is arranged such that the reactionzone does not begin until water has flowed a predetermined distancealong the cathode. This is to promote laminar flow in the cathode flowpath through the reaction zone. In a preferred embodiment this isachieved by the cathode being placed in the water flow path with theleading edge of the cathode at a shorter distance from the inlet thanthe leading edge of the anode. With this arrangement the water flowacross the cathode plate has an opportunity to settle before thereaction zone, since the electrical reaction will not commence until theflow reaches an area where the anode and the cathode are sufficientlyclose together. For example, the leading edge of the cathode may beplaced between 20 mm and 60 mm closer to the water inlet than theleading edge of the anode. In the preferred embodiment the leading edgeof the cathode is placed about 30 mm closer to the water inlet than theleading edge of the anode.

The incoming water may be permitted to flow a predetermined distancewithout disturbance after the end of the flow conditioning elements andbefore the water reaches the cathode or the anode. This undisturbed flowhelps the water recover from any disruptive effects arising from theprevious the flow conditioning elements or from the termination of thoseflow conditioning elements. For example, the water may flow undisturbedfor at least 5 mm before reaching the leading edge of the cathode or theanode, preferably at least 10 mm. The greater the distance, the moreopportunity there is for the flow to settle into a laminar flow pattern.However, typically there will be a point where increasing the distancedoes not provide a corresponding increase in the uniformity of the flowpattern. With a slot width of about 2 mm good results have been seenwhen the water flows undisturbed for about 10 mm before it reaches theleading edge of the cathode or the anode. When the electrodialysis unitis formed of repeated cathode and electrode plates separated bymembranes the area of undisturbed flow may be formed as an undisturbedflow path in a space between two membranes, this undisturbed flow pathextending for the predetermined distance between the membranes beforethe water reaches the leading edge of cathode or the anode locatedbetween the two membranes.

Where the electrodialysis unit includes a layered electrode stack asdescribed above the electrodialysis unit preferably includes a flowdistribution system for distributing the incoming water to eachelectrode chamber in equal amounts. Hence, the electrodialysis unit mayinclude a cathode flow distribution system for distributing incomingwater equally to each cathode water inlet and an anode flow distributionsystem for distributing incoming water equally to each anode waterinlet. As noted above, the cathode flow paths may receive a greater flowrate of water than the anode flow paths. The cathode flow distributionsystem ensures that the cathode flow paths and at each of the multiplecathodes are supplied with a equal water flow. The anode flow paths aresimilarly supplied with a equal water flow.

The flow distribution system in a particularly preferred embodimenttakes the form of an inlet manifold for the anode flow paths and/orcathode flow paths wherein the inlet manifold comprises a first tubeprovided with holes along its length, the holes being connected to theflow paths, and a second tube located within and enclosed by the firsttube, the second tube having an inlet at one end and being closed at itssecond end and the second tube being provided with holes along itslength that open into the first tube. Further features of a preferredinlet manifold are discussed below.

Viewed from a second aspect the invention provides a method comprisinguse of the electrodialysis unit described above for the treatment of seawater, preferably use for treatment of ballast water.

Viewed from a third aspect the invention provides a method ofmanufacturing an electrodialysis unit comprising the steps of: providinga cathode, an anode, a membrane between the cathode and the anode, acathode flow path for water flow along the membrane on the cathode side,an anode flow path for water flow along the membrane on the anode side,and a reaction zone formed between the membrane and the cathode wherethe cathode faces the anode; arranging the cathode flow path for laminarflow in the reaction zone; and arranging flow conditioning elements inan area of incoming water flow to promote laminar flow in the incomingwater flow preceding the reaction zone.

The method may comprise providing features of the electrodialysis unitas set out above in relation to preferred features of the first aspect.

Viewed from a fourth aspect the present invention provides anelectrodialysis unit comprising: a plurality of cathodes, a plurality ofanodes and a plurality of membranes; wherein the cathodes and anodes arearranged alternately in an electrode stack, with membranes in betweeneach cathode and anode; and wherein the cathode and the anode are eachformed of a single conductive plate such that both surfaces of thecathode plates and anode plates enclosed within the electrode stack are,in use, in conductive contact with the water being treated.

In conventional electrodialysis units of this type the electrodes aremade from two pieces of titanium that are brazed to copper rods to forma sandwich. These copper rods then extend out of the electrodialysisunit and are used to provide connections to the main electrical supply.In the electrodialysis unit of this aspect a single conductive plate isused for each electrode. As a consequence the electrodialysis unit canbe made smaller and more compact. In addition, since the conductivematerial is typically relatively expensive, the reduction in the numberof plates used leads to cost savings. Titanium is used for the anodeplates and the cathode plates in preferred embodiments of theelectrodialysis unit.

By a single conductive plate it is meant that the main conductive andelectrically active part of the electrode is formed of a single plate,as compared to two plates as in the prior art discussed above. Theelectrodes may include other elements in addition to the singleconductive plate, such as fixing parts, shaped end portions and so on.

The electrodes may be arranged in a continuous electrode stack to formthe entire electrodialysis unit. However, this arrangement lends itselfto a parallel connection of all the electrodes to the electrical supply.It can be advantageous to allow for a series connection of parts of theelectrodialysis unit, for example for impedance matching with the powersupply. Hence, in a preferred arrangement the electrode stack comprisesmultiple sets of electrodes, with each electrode in a single setconnected in parallel, and each set of electrodes connected in series.For example an electrode stack made up of fifty anode chambers and fiftycathode chambers may be made up of five sets each comprising ten anodechambers and ten cathode chambers.

Within the centre parts of the electrode stack or of each set ofelectrode chambers, both surfaces of each conductive plate are inelectrical contact with the water, so both surfaces of the electrodesare utilised as active surfaces in the electrodialysis process. Theelectrodialysis unit comprises a repetition of the sequence: cathode,membrane, anode, membrane, with both sides of each electrode plate beingutilised, aside from the electrodes at the outer ends. The electrodes atthe outer ends of each set of electrodes in the electrode stack arepreferably both cathodes. The cathode can be cheaper to produce than theanode since the anode reaction requires an expensive coating for theelectrode. Hence, by the use of additional cathodes as the endelectrodes (for which only one side of the electrode is utilised in thereaction) the electrodialysis unit can be cheaper to produce withoutreducing the total reaction area.

The electrical connections for the electrodes may be made directly tothe conductive material of the conductive plates. Preferably theconductive plates are allowed to extend outside of the reaction area ofthe electrodialysis unit to provide electrical connection points.

In a preferred embodiment, the conductive plates that form theelectrodes are clamped between and supported by non-conductiveseparators. The separators may be for separating the fluid flow into andout of the cathode flow paths and anode flow paths. The separators mayinclude openings exposing the conductive plates in the reaction zones.The membrane can be placed across these openings between anode andcathode to complete the membrane cell where the electrodialysisreactions occur.

The separators preferably include inlet passages for incoming water andoutlet passages for outgoing diluate and concentrate. Flow guidefeatures are also preferably incorporated in the separators, such asflow conditioning elements as discussed above in relation to the firstaspect. Since the separators include flow guide features they aregenerally of larger size than the conductive plates.

Preferably, the conductive plates are provided with a seal that isbonded to the conductive plates and forms a shape corresponding to theshape of the separators. Since the separators are larger than theconductive plates the seal may extend beyond the edges of the conductiveplates. For example, the conductive plates may be generally rectangular,and the seal may be bonded along two opposite sides of the rectangle andthen extend outwardly beyond the two remaining sides of the rectangle.When the conductive plate and seal are placed between two separators theseal forms an enclosed electrode chamber. The two separators may beclamped about the conductive plate by any appropriate means, for exampleby a frame enclosing the electrode stack or by screws joining togethereach pair of separators.

The seal may be any suitable material, i.e. a resilient and waterresistant material. A rubber material is preferred. Preferably, the sealcomprises a rubber material. A high density rubber containing arelatively high level of filling-agent may be used.

It has been found that it may be difficult to securely attach the sealto the electrode, especially when a titanium electrode is used. In apreferred arrangement this problem is overcome by the use of athermosetting or vulcanising rubber, which is applied to the electrodeprior to heat treatment, and then bonded to the electrode by heating andoptionally pressurising the rubber to perform the thermosetting orvulcanising process whilst it is in contact with the electrode. Thesurface of the electrode may be conditioned prior to application of theuntreated rubber, for example by etching or other chemical process.

As discussed above in relation to the first aspect, preferredembodiments utilise different flow rates for the cathode and the anode.Consequently, the electrodialysis unit of this embodiment preferablyincorporates alternate separator designs for the cathode and the anode.This enables different flow guide features to be used for the anode andthe cathode. Also, since in the preferred embodiments the anode andcathode may have leading edges that are placed at a different distancefrom the respective water inlets, the different separator designs mayalso allow for support of the anode and cathode plates at the requiredpositions.

In preferred embodiments the unit includes cathode chambers comprisingfirst and second cathode separators located on either side of a cathodein the form of a conductive plate. The unit may include anode chamberscomprising first and second anode separators located on either side ofan anode in the form of a conductive plate. The electrodialysis unit maythen be formed by a sequence of anode and cathode chambers, withmembranes between each chamber.

The separators may include through holes that, when a number ofelectrode chambers are stacked together, form water inlet and outletpassages. There may be one or more anode inlet passage and anode outletpassage. Similarly there may be one or more cathode inlet passage andcathode outlet passage. In a preferred embodiment, to provide anincreased flow rate through the cathode, there are two cathode inletpassages, one anode inlet passage, two cathode outlet passages and oneanode outlet passages, each of about the same size. Seals are preferablyprovided about the through holes to maintain separation of the anodefluid and cathode fluids. Tubes may be passed along the through holes ofall the separators in the stack to complete the inlet and outletpassages. The tubes may be inlet manifolds as described below.Advantageously, the use of tubes along through holes can also act toalign the chambers in the electrode stack.

Viewed from a fifth aspect the invention provides a method comprisinguse of the electrodialysis unit described above for the treatment of seawater, preferably use for treatment of ballast water.

Viewed from a sixth aspect the invention provides a method ofmanufacturing an electrodialysis unit comprising a plurality ofcathodes, a plurality of anodes and a plurality of membranes; the methodcomprising arranging the cathodes and anodes alternately in an electrodestack, with membranes in between each cathode and anode; wherein thecathode and the anode are each formed of a single conductive plate suchthat within the electrode stack both surfaces of the cathode plates andanode plates are, in use, in conductive contact with the water beingtreated.

The method may include providing a seal and bonding the seal to theconductive plates. In a preferred embodiment a thermosetting orvulcanising rubber is used for the seal, and the method comprisesapplying the rubber to the electrode prior to heat treatment, and thenbonding the rubber to the electrode by heating and optionallypressurising the rubber to perform a thermosetting or vulcanisingprocess whilst it is in contact with the electrode. The surface of theelectrode may be conditioned prior to application of the untreatedrubber, for example by etching or other chemical process.

Preferably, the method includes clamping the conductive plates and theseal between non-conductive separators. The two separators may beclamped about the conductive plate by any appropriate means, for exampleby a frame enclosing the electrode stack or by screws joining togethereach pair of separators.

The separators may be for separating the fluid flow into and out of thecathode flow paths and anode flow paths. The separators may includeopenings exposing the conductive plates in the reaction zones.Preferably, the method comprises placing membranes across these openingsbetween anode and cathode, such that the membranes are sandwichedbetween adjacent electrodes.

The separators may include through holes that, when a number ofelectrode chambers are stacked together, form water inlet and outletpassages. There may be one or more anode inlet passage and anode outletpassage. Similarly there may be one or more cathode inlet passage andcathode outlet passage. The method preferably comprises passing tubesalong the through holes of all the separators in the stack to completethe inlet and outlet passages. Advantageously, the use of tubes alongthe through holes can also act to align the chambers in the electrodestack.

The method may comprise steps as discussed above in relation to thethird aspect. The method may comprise providing other features of theelectrodialysis unit as set out above in relation to preferred featuresof the first or fourth aspect.

Viewed from a seventh aspect the invention provides an electrodialysisunit comprising: a plurality of cathodes, a plurality of anodes and aplurality of membranes; the cathodes and anodes being arrangedalternately in an electrode stack, with membranes in between eachcathode and anode, anode flow paths formed between the membranes andanodes and cathode flow paths formed between the membranes and cathodes;the electrodialysis unit further comprising an inlet manifold fordistributing water to the anode flow paths or to the cathode flow paths,wherein the inlet manifold comprises a first tube provided with holesalong its length, the holes being connected to the flow paths, and asecond tube located within and enclosed by the first tube, the secondtube having an inlet at one end and being closed at its second end andthe second tube being provided with holes along its length that openinto the first tube.

By the use of this arrangement of nested tubes, water can be evenlydistributed to all flow paths along the electrode stack. In use, watermay flow through the inlet of the second tube, into and along the secondtube, out of the holes of the second tube into the first tube, andthereafter out of the first tube into the electrode stack. This waterpath and the flow restrictions from the holes act to maintain agenerally constant pressure along the length of the electrode stack andhence water is supplied evenly to all the anode/cathode flow paths.

The inlet manifold may be provided only for the cathode or only for theanode, but preferably similar inlet manifolds are provided for both thecathode and the anode. As discussed above, it is advantageous to have ahigher flow rate through the cathode flow paths than through the anodeflow paths. Therefore, preferably the electrodialysis unit comprises aninlet manifold for the cathode flow paths that is arranged for a higherflow rate than the inlet manifold for the anode flow paths. This may beachieved by a larger manifold. Preferably however the unit comprises twoparallel inlet manifolds for the cathode flow paths, supplying water inparallel to the flow paths. When there is just one similar inletmanifold for the anode flow paths, this enables approximately double theflow rate for the cathode flow paths compared to the anode flow paths.

The tubes of the manifold are preferably circular. A circular tube iseasy to obtain and/or manufacture, and in addition it is straightforwardto form holes for mount a circular manifold. However, the tubes of theinlet manifold are not limited to circular tubes and could for examplebe tubes with a rectangular cross-section or another tube shape.

The holes of the first tube preferably connect to the flow paths viaflow guides, for example flow conditioning elements as discussed above.The holes of the first tube may take the form of slits locatedtransversely across the tube.

The holes of the second tube may be slits located transversely acrossthe tube. The second tube may have holes on a first side facing theholes of the first tube. There may also be additional holes on theopposite side.

Preferably the second tube is located within the first tube at a centrallocation, i.e. the first and second tube may be concentric.

In a preferred embodiment, the anodes and cathodes are supported byseparators and the separators are provided with through holes, whereinthe inlet manifold is located along through holes in the separators andpreferably wherein the holes in the first tube open into flow guidefeatures formed in the separators. The first tube may be a tube formedby alignment of through holes in the separators. The second tube may bea pipe inserted into the first tube.

In preferred embodiments, the electrodialysis unit has features asdiscussed above in connection with the first or fourth aspects.

Viewed from an eighth aspect the invention provides a method comprisinguse of the electrodialysis unit described above for the treatment of seawater, preferably use for treatment of ballast water.

Viewed from a ninth aspect the invention provides a method ofmanufacturing an electrodialysis unit comprising: a plurality ofcathodes, a plurality of anodes and a plurality of membranes; thecathodes and anodes being arranged alternately in an electrode stack,with membranes in between each cathode and anode, anode flow pathsformed between the membranes and anodes and cathode flow paths formedbetween the membranes and cathodes; the method comprising providing aninlet manifold for distributing water to the anode flow paths or to thecathode flow paths, wherein the inlet manifold comprises a first tubeprovided with holes along its length, and a second tube having an inletat one end and being closed at its second end and the second tube alsobeing provided with holes, the method further comprising providing thefirst tube in the electrode stack so that the holes of the first tubeconnect to the flow paths and locating the second tube within the firsttube so that the second tube is within and enclosed by the first tubeand the holes of the second tube open into the first tube.

In a preferred embodiment, the anodes and cathodes are supported byseparators and the separators are provided with through holes, themethod comprising providing the inlet manifold in the electrode stackalong through holes in the separators.

The method may comprise steps as discussed above in relation to thethird or sixth aspect. The method may comprise providing other featuresof the electrodialysis unit as set out above in relation to preferredfeatures of the first or fourth aspect.

Viewed from a tenth aspect the invention provides an electrodialysisunit for treating water comprising: a membrane cell, a temperaturemonitoring device for monitoring the temperature of incoming water and aheater for increasing the temperature of the incoming water before itreaches the membrane cell, wherein the heater is arranged to operate toincrease the temperature of the incoming water when the original watertemperature is below a predetermined level.

It has been found that a temperature of the incoming water below acertain level leads to a significant increase in electrical powerrequired to drive the electrodialysis unit. This increase in power canbe less than the power required to heat the water. Hence, the efficiencyof the system is improved by heating the water when the originaltemperature is too low.

The electrodialysis unit is preferably for the treatment of sea water,more preferably for treatment of ballast water. The electrodialysis unitmay be for installation on a vessel such as a ship.

The heater may be an electrically powered heater or a fuel heater.Preferably however the heater is powered by waste heat, which may forexample be provided by waste heat from an engine cooling system or byheat recovered from an engine exhaust. This further improves theefficiency. The heater may include a heat exchanger or similar device.

In a preferred embodiment the heater is operated to increase thetemperature of the incoming water when the original temperature is below10° C., more preferably when the original temperature is below 15° C.and yet more preferably when the temperature is below 16° C. It has beenfound that for sea water a significant increase in power usage occurswhen the temperature drops below 16° C. Preferably the water is heatedto above 16° C., more preferably to at least 18° C. and optionally to20° C. or above. It has been found that for sea water there are nosignificant reductions in power usage for temperatures in excess ofabout 20° C.

Viewed from an eleventh aspect the invention provides a method oftreating water by electrodialysis using a membrane cell, the methodcomprising: monitoring the temperature of incoming water and increasingthe temperature of the incoming water before it reaches the membranecell if the original water temperature is below a predetermined level.

Preferably the method is a method of treating sea water, more preferablya method of treating ballast water. The method may be for treatment ofballast water on board a vessel such as a ship.

The step of heating the water may use a heater. The heater may be anelectrically powered heater or a fuel heater. Preferably however themethod comprises heating the water by using heat, which may for examplebe provided by waste heat from an engine cooling system or by heatrecovered from an engine exhaust.

A preferred embodiment comprises increasing the temperature of theincoming water when the original temperature is below 10° C., morepreferably when the original temperature is below 15° C. and yet morepreferably when the temperature is below 16° C. Preferably the water isheated to above 16° C., more preferably to at least 18° C. andoptionally to 20° C. or above.

Viewed from a twelfth aspect the invention provides a method ofmanufacturing an electrodialysis unit comprising providing a membranecell, providing a temperature monitoring device for monitoring thetemperature of incoming water, and providing a heater for increasing thetemperature of the incoming water before it reaches the membrane cell,the heater being arranged to operate to increase the temperature of theincoming water when the original water temperature is below apredetermined level.

The electrodialysis units and methods of the aspects and preferredembodiments described above may be combined. The electrodialysis unitsof the aspects and preferred embodiments described above may include oneor more of the following features and/or may be incorporated in a watertreatment apparatus including any of the following features.

The membrane may be any suitable membrane for use in the electrodialysisof water, such as a water impermeable ion-exchange membrane. An ionselective membrane may optionally be used, for example if the membranecell is to be powered by AC electricity.

The electrodialysis treatment is preferably applied to only a part ofthe water to be treated, with this part being separated from the mainbody of the water and a product of the electrodialysis unit beingreturned to the remainder of the water to treat the entirety of thewater. In a preferred water treatment apparatus the part of the watertreated by the electrodialysis unit is preferably separated from theincoming water flow just prior to treatment and then passed through theelectrodialysis unit as the remainder of the water passes by withoutbeing treated by the electrodialysis unit. Thus, the apparatus mayinclude a main flow path, wherein the inlet flow path is arranged toseparate a portion of the flow from the main flow path and direct itthrough the electrodialysis unit. Alternatively, the part of the watertreated by the electrodialysis unit can be provided from a separatesource, for example an external source of brine or saltwater. In bothcases, the apparatus may include a connection from the outlet flow pathto a main flow path, wherein the outlet flow path added the product ofthe electrodialysis unit to the main flow path.

The water which is not treated by the electrodialysis unit can beexposed to other treatments, effectively in parallel with theelectrodialysis treatment to the said part of the water, for example acavitation treatment or a nitrogen injection treatment as discussed inmore detail below.

Preferably less than 10% by volume of the total water flow into thetreatment apparatus passes through the electrodialysis unit, morepreferably less than 5% and yet more preferably less than 2%. An amountof about 1.6% by volume is preferred, although depending on conditions,amounts as low as 1% or 0.5% could be used. It is possible to manipulatethe necessary flow volume by altering the current used in theelectrodialysis unit and the salinity of the water. Thus, depending onthese factors and the particular application of the treatment, the flowvolume used can be larger or smaller.

In preferred embodiments, the invention is a ballast water treatmentapparatus. As discussed above, water treatment of this type isparticularly desirable for ballast water. Many existing water treatmentsare not suitable for ballast water treatment due to the high volume ofwater that needs to be treated in a short space of time. As only a partof the water needs to be passed through the electrodialysis unit, withthe remainder of the water not passing through the electrodialysis unit,the treatment can be applied to a much higher volume of water in a giventime than alternatives which require the entirety of the water to bedirectly affected by an electrical treatment.

The electrodialysis unit may be for producing a diluate stream and aconcentrate stream at the cathode and anode respectively, with theproduct of the electrodialysis unit that is returned to the water beingcomposed of some or all of one or both of these streams. The product ofthe electrodialysis unit may simply be some or all of the concentratestream produced by the electrodialysis unit. However, preferably theproduct of the electrodialysis unit is a mixture of some or all of theconcentrate stream, ideally a major portion thereof with at least aportion of the diluate stream, ideally in a smaller amount than theamount of concentrate. The concentrate stream contains an increasedcontent of different oxidants and the oxidants are particularlyeffective at killing or disabling micro-organisms in the water when theproduct of the electrodialysis unit is returned to the main water flow.

After the electrodialysis treatment, the concentrate may have a lower pHthan the water prior to treatment, and the diluate may have a higher pH.Mixing the concentrate with some or all of the diluate allows the pH ofthe product of the electrodialysis unit to be adjusted.

In a preferred embodiment the concentrate stream and at least a portionof the diluate stream are mixed immediately after passing through theelectrodialysis unit. This may be done by removing a portion of thediluate stream, and then mixing the remainder of the diluate with theconcentrate stream. The amount of diluate removed may be between 20% and80% by volume In alternative preferred embodiments, the product of theelectrodialysis unit that is returned to the main water flow is all ofthe diluate stream along with all of the concentrate stream. It has beenfound that in some circumstances the entirety of the diluate is requiredto provide the desired pH and other characteristics of the final waterflow after the product of the electrodialysis unit is mixed in. In thiscase, the diluate and the concentrate may react together to consume alloxidants and reactive products from the water. However, reactions tokill micro-organisms will also occur before all the oxidants andreactive products are consumed by reaction of the diluate andconcentrate. Moreover, the electrodialysis process is not completelyreversible. For example, the reaction may produce gasses such ashydrogen and chlorine which exit the water.

In order to control the mixing ratio pH is monitored and balancing iscontrolled to keep pH in the desired range. The pH monitoring may be bymeans of a pH electrode. Preferably, the pH is maintained below 6, forexample within a range from 4 to 6, typically at a pH of about 5. Themixing ratio and the pH of the product of the electrodialysis unit maybe controlled by varying the amount of diluate added to the concentrate,for example by varying the amount of diluate removed prior to mixing.Control of the pH may also occur by controlling the current or voltagesupplied to the electrodialysis unit, to thereby vary the strength ofthe resultant electrodialytic effect and hence vary the oxidativestrength of the concentrate.

The apparatus may include a diluate removal flow path for removing apart of the diluate stream. To facilitate mixing of the concentrate andnon-removed diluate the apparatus may include a mixing area prior to theoutlet flow path. In one preferred embodiment, the mixing area is abuffer tank. Alternatively, the concentrate and diluate may be mixed asthey flow through the outlet flow path. Mixing may occur at the sametime as the concentrate stream and non-removed part of the diluatestream are mixed with the main flow, i.e. the product of theelectrodialysis unit may consist of two parts which are only mixed whenthese two parts are mixed with the rest of the water. Mixing may bepromoted by a static mixer or turbulence inducing means in the mixingarea or in the outlet flow path.

The removed diluate may be re-injected to the water upstream prior tothe electrodialysis unit. If other treatment stages are included in awater treatment apparatus, such as a cavitation treatment or filtrationtreatment then the remainder of the diluate is preferably re-injectedprior to other treatment stages and even prior to the ballast pump.Re-injecting the diluate avoids the need to dispose of it. The diluatewill also advantageously act as a cleaning agent, in particular for thefiltering processes if it is injected prior to filtering.

The characteristics and amounts of concentrate and diluate reinjectedinto the main flow may be controlled by monitoring Oxygen ReductionPotential (ORP) and/or the consumption of Total Residual Oxidant (TRO).The ranges for desired values of ORP may be 250-800 mV, more preferably300-500 mV. The immediate initial values of TRO following reinjection ispreferably between 1 and 10 mg CI/L more preferably between 2 and 5 mgCI/L dropping rapidly to 0.01-1 mg CI/L after a period of 1 to 36 hourstypically. The consumption of TRO is strongly dependent upon thecharacteristics of the water to be treated. To optimise the performanceof the electrodialytic unit, it is desirable to arrange a calibrationflow loop allowing presetting of current and mixing ratios prior toinitiating actual water treatment. When the ORP and/or TRO measuredvalues are outside the desired ranges, then the operation of theelectrodialysis unit is adjusted accordingly.

To direct the water flow, the apparatus may comprise conduits, pipes,baffles and the like. The electrodialysis unit may be integrated into aflow path for the main water flow, and thus the apparatus may include amain flow pipe or conduit for the main flow, with smaller pipes orconduits or the like for channelling a part of the main flow through theunit. Alternatively, the electrodialysis unit may be provided as astandalone unit which can be connected to an existing water conduit totreat the water therein. In this case, the treatment apparatus mayinclude suitable pipes or conduits for connection of the standalone unitto the existing conduit, along with valves, dosage pump(s) and so on asrequired.

An independent source of brine may be used to augment the inputelectrolyte for the electrodialysis unit and increase its salinity. Thismight for example be brine produced as a by-product of freshwaterproduction or in a dedicated brine production plant, such as a reverseosmosis plant. A recirculating reverse osmosis plant may be used togenerate a saturated brine solution for use as an addition to the inputelectrolyte. The addition of brine or the like is required when thesystem is used to treat fresh water or weakly brackish water, asotherwise the electrical treatment will not be effective due to a lackof ions in the water. Brine may be also added to sea water with a lowsalt content in order to bring the salt content of the electrolyte to amore preferred level. At lower salt contents a larger electrical currentis required to achieve the same treatment effect with theelectrodialysis unit. Consequently, by increasing the salt content areduction in energy usage can be obtained. As an example, in the NorthSea a salinity of 25 parts per thousand or higher is typical, whereas inthe Baltic Sea surface waters have a much lower salinity, of perhaps 7parts per thousand. Preferably, brine is added to the input electrolyteto the electrodialysis unit to maintain a salinity of at least 25 partsper thousand.

Preferably, the water is stored for a period of time in a reservoir ortank after treatment. This allows time for the oxidants and reactivesubstances from the product of the electrodialysis unit to have fulleffect on any micro-organisms and other unwanted matter in the water. Ina particularly preferred embodiment, the invention is used in ship'sballast water treatment, wherein the water is treated as it is taken into the ballast tanks, and then it is stored in the ballast tanks beforedischarge. In this circumstance there is generally a reasonable time ofstorage as the ship moves from port to port before re-loading with cargoand discharging the ballast water. This time can be advantageously putto use in allowing the treatment by the product of the electrodialysisunit to take effect.

The treatment flow path may be formed by a conduit external to the mainflow path. This allows an existing water flow path to be easily adaptedto include the treatment apparatus by the addition of an appropriateinlet and outlet junction. Alternatively, the treatment flow path may beintegrated with the main flow path as a single unit.

The water treatment apparatus may optionally include a gas injectionunit for injecting nitrogen gas into the water prior to or at the sametime as the product of the electrodialysis unit is returned to thewater. In some cases, it is preferred to inject the nitrogen immediatelyafter the product of the electrodialysis unit is returned to the water.The nitrogenation of the water is thought to prolong the oxidanttreatment, and also has a beneficial corrosion reduction effect.

Nitrogen may be injected into all or a part of the water flow asdiscussed in WO 2008/047084. The nitrogen is preferably injected insufficient amounts to ensure that the treated water is super-saturatedwith nitrogen. In a preferred embodiment, a part of the water flow isseparated from the main flow, and nitrogen is injected into this part.Preferably the part of the water flow is less than 15% of the wholevolume of water flow. When the nitrogenated water flow is reintroducedto the main water flow, a static mixer may be used to promote mixing ofthe two water flows.

The water treatment apparatus may optionally include a cavitation unitfor applying a cavitation treatment to the water. The use of acavitation unit produces a physical effect on any micro-organisms andother living and non-living matter in the water and thus breaks downthese unwanted elements. Preferably, the cavitation unit is placed totreat water before the electrodialysis treatment is applied. Theoptional cavitation treatment can thus be used to eliminate larger andmore complex organisms, as well as breaking down other unwanted matter,and in particular breaking down groups or clumps of micro-organisms.This can provide a pre-treatment for the treatment effect of theelectrodialysis unit, since the damaged and broken down organism aremore easily attacked by the product of the membrane cell can thenprovide a final level of treatment which eliminates any remainingorganisms, and is able to act more effectively due to the fact thatlarger sized organisms and groups of organisms have been broken down.

An alternative pre-treatment or additional pre-treatment may optionallybe provided by an electrical treatment unit that applies high frequencyalternating electrical current to the water, the frequency beingsufficiently high to physically damage micro-organisms in the water. Theelectrical treatment unit may comprise electrodes in contact withflowing water. By sufficiently high, it is meant that the frequency ishigh enough to provide a physical effect on the micro organisms. Forexample, a frequency of at least 50 Hz may be used, preferably afrequency of at least 500 Hz and more preferably at least 1 kHz.Preferably the frequency is sufficiently high to damage or weaken thecell walls, membranes or nuclei of the organisms.

The electrodes may be connected in 1-phase or 3-phase configurations.The applied frequency may be of a characteristic where the frequencyalters, for example a sweeping frequency or noise pattern. Preferably amoderate voltage is used, for example for a 1-phase configuration avoltage of less than 120 volts may be used. Avoiding high voltagesavoids the risk of electrocution and other hazards associated with highvoltages.

The methods of the various aspects described above may, in preferredembodiments include method features corresponding to the preferredapparatus features discussed above. The method may be for the treatmentof ballast water, and the method preferably comprises: treating thewater used to fill the ballast tank in accordance with any aspect orpreferred embodiment set out above, optionally injecting nitrogen intothe water, storing the treated water in the ballast tank, dischargingthe water from the tank, optionally treating the discharged water byinjecting an oxygen containing gas, optionally applying a repeatedmicro-organism killing action to the water, and releasing the water tothe environment.

By treating the water as it enters and leaves the tank the risk ofstoring and releasing undesirable matter, in particular micro-organismsand other organic matter, is greatly reduced, as the various treatmentsteps result in such matter being broken down to a non-hazardous state.The optional injection of nitrogen into water which is then storedreduces corrosion of the ballast tank by reducing the amount ofdissolved oxygen in the water. In addition, this reduces weathering ofcorrosion protection systems such as coatings and paints as oxidation isa cause of such weathering.

Preferred embodiments of the invention will now be described by way ofexample only and with reference to the accompanying drawings in which:

FIG. 1 shows a ballast water treatment system with an electrodialysisunit,

FIG. 2 illustrates an electrodialysis unit including a stack ofelectrodes,

FIG. 3 shows a single electrode chamber as used in the unit of FIG. 2,

FIG. 4 shows an electrode plate and seal,

FIG. 5 is a partial cutaway view of an electrodialysis unit in which theflow distributor can be seen,

FIG. 6 is a perspective view of the internal tube of the flowdistributor,

FIG. 7 is a partial view of a separator showing the flow conditioningelements,

FIG. 8 is a schematic wireframe drawing showing further detail of theflow distributor and flow conditioning elements,

FIG. 9 is a cross-section through a portion of two cathode chambers andone anode chamber showing the leading edges of the electrodes,

FIG. 10 shows a plot of velocity across each of the cathode chambersalong the electrode stack in a computer model when the preferred flowdistributor is not used,

FIG. 11 shows a plot of velocity across each of the cathode chambersalong the electrode stack in a computer model when the preferred flowdistributor is used,

FIG. 12 shows a plot of velocity across the width of a cathode flow pathin a computer model when the preferred flow conditioning elements arenot used, and

FIG. 13 shows a plot of velocity across the width of a cathode flow pathin a computer model when the preferred flow conditioning elements areused.

The arrangement of FIG. 1 utilises an electrodialysis unit within aballast water treatment system, but it will be appreciated that otheruses for the preferred electrodialysis unit exist, and that theelectrodialysis unit can be adapted to suit different requirements. Inparticular, it should be understood that the electrodialysis unitdescribed herein can be used in ballast water treatment, or in otherwater treatment applications, without the need for combination withother treatment types as shown in the exemplary arrangement of FIG. 1.

FIG. 1 thus illustrates a ballast water treatment system that includesan electrodialysis unit 8. In this example, the water is filtered andthen treated by a cavitation unit 10, a gas injection unit 14 and theelectrodialysis unit 8. This series of treatments causes damage anddeath to the organisms in the water. As well as affecting organisms inthe water, nitrogen added to the water at the injection unit 14 reducesthe level of dissolved oxygen in the water and reduces the potential ofre-growth of organisms as well as reducing the weathering of coatingsand the speed of corrosion. Furthermore, the reduction in oxygen isthought to prolong the effect of oxidants introduced into the water viathe product of the electrodialysis unit 8. By controlled atmospheremanagement when the ballast tanks are empty by using nitrogen, theseeffects are enhanced further.

During filling of the ballast tanks, ballast water is pumped from thesea through an inlet pipe 1 by the use of the ship's ballast pump system2. After the pump 2, water flows through a pipe and is filtered througha first filter 4, which filters larger particles from the water. Theseform a sludge which is discharged at the point of ballast uptake.

Downstream of the first filter 4, a pressure booster may optionally beinstalled. The pressure booster can be used to maintain the level ofwater pressure needed for successful treatment in the units furtherdownstream.

In this example, water then continues to flow into the cavitation unit10. In the cavitation unit 10 hydrodynamic cavitation is induced by arapid acceleration of the fluid flow velocity, which allows the fluidstatic pressure to rapidly drop to the fluid vapour pressure. This thenleads to the development of vapour bubbles. After a controlled period oftime which allows bubble growth, a rapid controlled deceleration thenfollows. This causes the fluid static pressure to rise rapidly whichcauses the vapour bubbles to violently collapse or implode exposing anyorganisms or the like in the water to the high intensity pressure andtemperature pulses, which breaks down the organisms in the water.

After the cavitation unit 10, a part of the water flows through theelectrodialysis unit 8. The remainder of the water is not treated by theelectrodialysis unit 8, and can simply continue to flow along a pipe orconduit to the later treatment stages. In the embodiment of FIG. 1 theelectrodialysis unit is fitted externally to the main flow conduit, andthus could be retro-fitted to an existing treatment system.

In an alternative embodiment, instead of or in addition to the treatmentof incoming ballast water by the electrodialysis unit 8, another sourceof brine or saltwater 24 can be used as the input electrolyte for theelectrodialysis unit 8. This could, for example, be brine produced as aby-product in a ship's freshwater production.

The electrodialysis unit 8 of the preferred embodiment is provided witha temperature control system 9. This is used to ensure that the waterutilised by the electrodialysis unit 8 does not drop below a settemperature. The temperature control system 9 includes a temperaturemonitoring device 9 a for monitoring the temperature of incoming waterand a heater 9 b for increasing the temperature of the incoming waterbefore it reaches the membrane cell of the electrodialysis unit 8, Theheater 9 b is arranged to operate to increase the temperature of theincoming water when the original water temperature is below apredetermined level. In this embodiment the predetermined level is 16°C. If the temperature of the incoming water is below 16° C. then thewater is heated up to about 20° C. using the heater. The heater 9 b useswaste heat from the ship's engines.

The electrodialysis unit 8, which is described in more detail below withreference to FIGS. 2 to 9, produces a diluate stream 11 and aconcentrate stream 12. These two streams progress to a pH balancer ormixing unit 13, which produces a product 17 of the electrodialysis unit8 that is directed back into the main water flow, and depending on thecomposition of the product 17, the mixing unit 13 may also give out aresidue of diluate 18. The mixing unit 13 includes a pump or the like tocontrol the amount of diluate 11 which is added to the concentrate 12 toform the optimum product 17 of the electrodialysis unit 8.

Downstream of the point of injection of the product 17 of theelectrodialysis unit 8 there is a sampling and measurement point 15,which measures ORP and/or TRO and communicates the measured values tothe mixing unit 13. These measurements monitor the effect of theelectrodialysis unit 8 on the water and are used to control the mixingunit 13, for example by controlling a dosing pump.

The diluate residue 18 may be reinjected into the incoming water priorto all treatment steps, and preferably also before the filter 4 and/orthe ballast water pump 2. Alternatively, it may be stored in a holdingtank 25 or ship's bilge water tank 26.

In the arrangement shown, the gas injection unit 14 treats the waterafter the product 17 of the electrodialysis unit 8 is returned to themain flow. However, in alternative arrangements the product 17 isreturned to the main flow downstream of the gas injection unit 14, withthe monitoring unit 15 likewise downstream of the gas injection unit 14,monitoring the water conditions after the product 17 has been mixed in.

In the gas injection unit 14, nitrogen gas 16 is injected into theincoming water using a steam/nitrogen injector or a gas/water mixer inorder to achieve the desired level of nitrogen super-saturation in thewater, which kills organisms and reduces corrosion by reducing theoxygen level. This also prolongs the treatment effect of the oxidants inthe water.

Downstream of the treatment units, treated water is distributed by theship's ballast water piping system 23 to ballast water tanks. Here,excess gas is evacuated until a stable condition is achieved. This isregulated by means of valves integrated with the tanks ventilationsystem. These valves ensure stable conditions in the tank during theperiod the ballast water remains in the tank, in particular a high levelof nitrogen super-saturation and a low level of dissolved oxygen in thewater. Maintaining the level of super-saturation leads to an ongoingwater treatment both by the super-saturation itself and also by oxidantsintroduced by the electrodialysis unit 8. The treatment thus results intreated water that continues to kill or disable any surviving organismswhilst the water is stored in the ballast tanks.

Water is then left to rest in the ballast water tanks. When the ballastwater is discharged, water flows through a discharge treatment processthat returns the oxygen content of the water to an environmentallyacceptable level for discharge. The water is pumped from the ballasttanks and passes through at least the gas injection unit 14. This isused to return oxygen to the water as air replaces nitrogen as theinjection gas. Optionally, the water may be re-treated by the cavitationunit 10 as it is discharged.

The operation of the electrodialysis unit 8 will now be explained. Anembodiment of the structural arrangement of electrodialysis unit 8 isdescribed below with reference to FIGS. 2 to 9. As discussed above,electrodialysis is an electro-membrane process where ions aretransported through ion exchange membranes in a fluid system. In thesimplest implementation of an electrodialysis unit a single membrane isplaced between two electrodes. An electric charge established byapplying a voltage between two electrodes allows ions to be driventhrough the membrane provided the fluid is conductive. The voltage isapplied by power connection points of a conventional type, which are notshown in the drawings. The two electrodes represent respectively theanode and the cathode. The electric charge creates different reactionsat the different electrodes. At the anode, the electrolyte will have anacidic characteristic whilst at the cathode, the electrolyte will becharacterised by becoming alkaline. Membranes used in electrodialysisare chosen for the ability to allow ion exchange whilst being liquidimpermeable. This allows the alkaline solution to be kept separate fromthe acidic solution.

Various reactions which occur in an electrodialysis membrane cell wherethe incoming electrolyte is ballast water taken from a ballast waterpipeline (i.e. sea water) are shown in Table 1 below. This includes areaction on the cathode side that produces brucite (Mg(OH)₂). Otherreactions will also occur since various compounds may be present in thewater in addition to sodium and magnesium salts.

TABLE 1 Reactions at the anode: Reactions at the cathode: 2Cl⁻ − 2e →Cl₂2H₂O + 2Na⁺ + 2e → 2NaOH + H₂ 2H₂O − 4e → 4H⁺ + O₂ 2H₂O + 2e → H₂ + 2OH⁻Cl₂ + H₂O → HClO + HCl O₂ + e → O₂ ⁻ HCl + NaOH → NaCl + H2 O₂ ⁻ + H⁺ →HO₂ Cl⁻ + 2OH⁻ − 2e → ClO⁻ + O₂ + H₂O + 2e → HO₂ ⁻ + OH⁻ H₂O 3OH⁻ − 2e →HO₂ ⁻ + H₂O O₂ + 2H₂ + 2e → H₂O₂ + 2OH⁻ HO₂ ⁻ − e →HO₂ H⁺ + e → H^(•)OH⁻ − e →OH^(•) H^(•) ⁺ H^(•) → H₂ OH^(•) ⁺ OH^(•) → H₂O₂ OH^(•) ⁺OH^(•) → H₂O₂ HClO + H₂O₂ →HCl + O₂ + H₂O₂ + OH^(•) → HO₂ + H₂O H₂OClO⁻ + H₂O₂ →¹O₂ + Cl^(•) + H₂O₂ 

 H⁺ + HO₂ ⁻ H₂O H₂O₂ + OH⁻ 

 HO₂ ⁻ + H₂O OH⁻ + HO₂ ⁻ 

 O₂ ² ⁻ + H₂O O₂ ²⁻ + H₂O₂ → O₂ ⁻ + OH⁻ + OH OH + H₂O₂ →H₂O OH⁻ +HCO³⁻ + Ca²⁺ = CaCO₃ + H₂O 2OH⁻ + Mg²⁺ = Mg(OH)₂

Table 2 below illustrates typical properties for an acidic solutionproduced at the anode and an alkaline solution produced at the cathode.The acidic solution forms the concentrate stream and the alkalinesolution forms the diluate stream.

TABLE 2 pH TRO (mg Cl/L) ORP (mV) Acidic solution (at the anode) 2-4400-1200 1100-1200 Alkaline solution (at the cathode) 11-14 — 800-900

The two separated streams are mixed in a ratio providing a product ofthe electrodialysis unit and optionally a residue with typicalcharacteristics shown in Table 3. The product is mainly concentrate fromthe anode, possibly with the addition of diluate to control the pHlevel. The residue will be formed of any diluate that is not mixed in tothe product. Typically the pH of the product in preferredimplementations of the electrodialysis treatment is between 4-6, buttreatment of the water will also occur within the broader pH range givenbelow.

TABLE 3 pH TRO (mg Cl/L) ORP (mV) Product  2-8.5 400-1000 750-800Residue 8.5-14 800-900

In order to tailor the chemical characteristics of the two streams,cross-treatment may be applied. This may constitute of an arrangementallowing all of or a portion of one or both streams to be re-injected atthe entrance to the opposite compartment to the compartment from whichit arrived from. Thus, the concentrate stream produced by the anodecould be cross-treated by re-injection into the cathode side of theelectrodialysis unit. The characteristics of the stream(s) expressed bypH, ORP and TRO may be further tailored by this method and enable theamount of residual diluate after mixing to be reduced if mixing isapplied in addition.

The mixing ratio will depend on the “quality” of the raw electrolyte,the size of the electrodes and the power applied.

The product of the electrodialysis unit enters the ballast water flow inconjunction with the point of injection of the N₂, preferablyimmediately behind, and thus is introduced into the water in conjunctionwith the process of super-saturation/oxygen removal. The residue, ifany, is injected upstream in the main flow immediately in front of thefilter.

FIGS. 2 to 9 illustrate an embodiment of an electrodialysis unit 8 thatcan be used to treat water. The electrodialysis unit may be used in theballast water treatment system of FIG. 1 or in any other appropriatewater treatment system. It can be used alone to provide a treatmenteffect, or alternatively it can be used in combination with other watertreatment devices.

FIG. 2 illustrates an electrodialysis unit 8 including a stack ofelectrode chambers 30 sandwiched between two end plates 32. Theelectrode stack is clamped between the end plates 32 by screws 34. Theelectrode chambers 30 are placed together in sets of ten membrane cellsseparated by insulating layers. The sets of electrode chambers 30 andplastic insulating layers can be seen more clearly in FIG. 5. Theelectrode chambers 30 are arranged in sets in this fashion to enable aseries connection of multiple sets of chambers 30. Water enters theelectrode stack via cathode water inlets 50 and an anode water inlet 52at the base of the electrode chambers 30 and then flows upward throughthe anode and cathode chambers. The water inlets 50, 52 are at thereverse side of the electrodialysis unit 8 in FIG. 2, but can be seen inFIG. 5 in which the unit 8 is shown from the opposite side. The diluatestream 11 from the cathode reaction and the concentrate stream 12 fromthe anode reaction exit the electrode stack via a concentrate outlet 36and diluate outlets 38. As discussed above, it is advantageous to have ahigher flow rate on the cathode side and so the preferred embodimentincludes two water inlet pipes for the cathode side and consequently twooutlet pipes 38 for the diluate, with only one concentrate outlet 36.Also shown in FIG. 2 are exposed ends 40 of the electrodes and theelectrical connection board 42 for the electrical supply to theelectrodes.

FIG. 3 shows a single electrode chamber 30. The unit 8 of FIG. 2consists of a large number of these electrode chambers 30 stackedtogether. The electrode chamber 30 includes a titanium electrode plate44 supported by and within two separators 46, which are placed one oneither side of the electrode 44. A rubber seal 48 extends around theouter edge of the separators 46 and provides a water tight barrierenclosing the electrode chamber 30. The exposed ends 40 of theelectrodes extend beyond the rubber seal 48 so that the electricalconnections 42 can be made outside of the reaction zone.

Water enters the electrode chamber 30 via through holes 54 at one endand exits via through holes 54 at the other end. The through holes 54are in fluid communication with the corresponding water inlets 50, 52and water outlets 36, 38. Each separator 46 has through holes 54 foreach of the three inlets 50, 52 and outlets 36, 38. Within the electrodechamber 30 the separators 46 are provided with flow guides for passageof water from the appropriate water inlet to the appropriate wateroutlet. Thus, the cathode electrode chamber will have flow guides totake water from the cathode water inlets 50 via the two outer throughholes 54 at the inlet side, direct it to pass across the cathode, andthen pass the diluate from the cathode reaction via further flow guidesto the outer through holes 54 on the outlet side and hence to thediluate outlets 38. The anode electrode chamber will have flow guides totake water from the anode water inlet 52 via the central through hole 54at the inlet side, direct it to pass across the anode, and then pass theconcentrate from the anode reaction via further flow guides to thecentral through hole 54 on the outlet side and hence to the diluateoutlet 36.

FIG. 4 shows an electrode plate 44 and seal 48 prior to attachment ofthe separators 46. The rubber seal 48 is bonded to the electrode plate44 along two sides as shown in the Figure. The seal 48 is also on bothfront and back surfaces of the electrode plate 44. The exposed end 40 ofthe electrode plate 44 extends beyond the seal along one side of theelectrode plate to permit electrical connection as set out above.

FIG. 5 is a partial cutaway view of an electrodialysis unit showingdetails of the flow distributor 56 for one of the cathode water inlets52. FIG. 5 also more clearly shows the five sets of membrane cellsseparated by plastic insulating layers. The construction of the membranecells is described in more detail below with reference to FIG. 9. InFIG. 5 one of the end plates 32 and each of the electrode chambers 30are partially cut away to expose a circular passage formed by alignedthrough holes 54 (also partially cut away). This circular passage formsa first tube 58 of the flow distributor 56. The first tube 58 can beseen more clearly in the wireframe diagram of FIG. 8, which shows moredetail of the fluid flow arrangement for the cathodes. The flowdistributor 56 also includes a second tube 60, located concentricallywithin the through holes 54. In FIG. 5 this second tube 60 is insertedfor one of the cathode inlets 50, but it is not shown for the othercathode inlet 50 or for the anode inlet 52. When the electrodialysisunit 8 is complete there is a second tube 60 in each water inlet, fittedconcentrically with each set of through holes 54.

The second tube 60 includes holes 62 along its length. These holes 62take the form of transverse slits cut on two sides of the second tube60, and placed at the upper and lower sides of the second tube 60 whenit is inserted in the first tube 58. FIG. 6 is a perspective view of thesecond tube 60 of the flow distributor 56 and shows further detail,including the holes 62 on the second, lower, side of the second tube 60.

Flow conditioning elements 64 on the separator 46′ for the cathodechamber are shown in FIG. 7A, which is a partial view of the lower partof a cathode separator 46′. The flow conditioning elements 64 are forevenly distributing the flow across the width W of the cathode flowpath.

The three through holes 54 would align with through holes 54 in otherseparators 46 in the electrode stack to form the first tubes 58 of theflow distributors. The second tubes 60, which are not shown in FIG. 7,would be inserted into the aligned through holes 54, with holes 62 inthe second tubes 60 allowing water to pass into the first tubes 58. InFIG. 7A since the separator 46 is for the cathode chamber the outerthrough holes 54 would be open to the cathode flow paths whereas thecentral through hole 54 would be sealed to prevent water from the anodeinlet 52 entering the cathode chamber. This sealing may be achieved byan O-ring seal placed about the central through hole. Holes would hencebe formed in the first tubes 58 at the two outer through holes 54 topermit water to pass from the water inlets 50, along the tubes 60, 58and then to the cathode reaction area via the flow conditioning elements64.

The flow conditioning elements 64 take the form of channels extendingaway from the through holes 54 in a fan shape in order to distributewater evenly across the entire width W of the cathode flow path. Thechannels are recessed into the separator 46′ and separated from eachother by walls 66. When the two separators 46′ that form the cathodechamber are joined together the walls 66 on each separator 46′ face eachother and come into contact so that the channels are sealed. Eachchannel has an end portion that is parallel with the flow directionthrough the cathode flow path. This helps reduce turbulence and promoteslaminar flow.

FIG. 7B is a similar partial view of a separator 46″ for the anodechamber. This anode separator includes flow conditioning elements 65 forthe anode flow path. As with the cathode flow conditioning elements 64the anode flow conditioning elements 65 take the form of channelsextending away from the through hole 54 in a fan shape in order todistribute water evenly across the entire width W of the anode flowpath. Since the anode flow path is supplied with water from only thesingle central through hole 54 the anode flow conditioning elements 65fan out over a larger angle than the cathode flow conditioning elements64. This allows water from flow distributor 56 in the central throughhole 54 to be evenly distributed over the anode flow path. The two outerthrough holes would be sealed, e.g. by an O-ring seal, to prevent wateringress from the cathode water supply. The anode flow conditioningelements 65 are recessed channels divided by walls 67. The flowconditioning part of the anode separator 46″ extends for a greaterdistance away from the through holes 54, since the leading edge of theanode is located at a greater distance from the water inlet, asdiscussed in more detail below with reference to FIG. 9.

FIG. 8 is a schematic wireframe drawing showing further detail of theflow distributor 56 and flow conditioning elements 64 for the cathodeflow paths in the electrode stack. The detail of the flow conditioningelements 64 is omitted for clarity, but the fan shapes can be seen. Eachcathode chamber has two symmetrical sets of flow conditioning elements64 that join in similar fashion to two flow distributors 56 in the twoouter through holes 54 of the separators 46. As discussed above, thethrough holes 54 are aligned to produce a first tube 58 of the flowdistributor 56. The first tube 58 connects to each of the sets of flowconditioning elements 64 via holes on an upper side. A second tube 60located concentrically within the first tube 58 supplies water to thefirst tube 58 from the two cathode inlets 50. Water passes between thefirst tube 58 and the second tube 60 via slit shaped holes 62 in upperand lower surfaces of the second tube.

The two tube flow distributor 56 acts to distribute water equally toeach cathode chamber along the length of the electrode stack 30. Theflow conditioning elements 64 provide even distribution of the wateracross the width W of each cathode flow path, and also promote laminarflow in the cathode flow paths.

For the anode chamber there is an arrangement similar to that shown inFIG. 8, but with water being distributed from only the central throughhole 54 instead of from the two outer holes 54. The anode water flowpath passes through a flow distributor 56 of identical design to theflow distributor 56 described above, using first and second tubes 58,60. This flow distributor 56 would be formed using a first tube 58created by the aligned central through holes 54 that connect to theanode water inlet 52.

After the incoming water passes through the flow distributors 56 andexits the flow conditioning elements 64, 65 it flows into the cathodeand anode flow paths within the cathode and anode chambers. At thispoint, as explained below with reference to FIGS. 10 to 13, the water isequally distributed to each flow path along the electrode stack andevenly distributed across the width W of each flow path. The equaldistribution of the water ensures an equal rate of reaction across eachmembrane cell in the electrode stack. The even distribution of wateracross each flow path width W means that the reaction occurs evenly overthe width of the electrodes, and also promotes laminar flow in thecathode flow paths.

FIG. 9 is a cross-section through a portion of two cathodes 68 and oneanode 70 at the point where water enters the cathode chambers andelectrode chamber. A membrane 71 is located between the electrodes toform the membrane cells. The Figure shows a partial cross-sectionthrough two complete membrane cells (one either side of the anode 70)and two partial membrane cells (at the outside portions of the twocathodes 68).

FIG. 9 illustrates further features used to promote laminar flow throughthe electrode chambers, especially in the reaction zone of the cathodeflow path. Incoming water for the cathode flow paths 72 arrives from theflow conditioning elements 64 of the separators 46′ as indicated by thearrow C. Water for the anode flow paths 74 arrives from the flowconditioning elements 65 as indicated by the arrow A. The water flowthrough the flow conditioning elements 64, 65 supplies two flow paths72, 74 that pass along each of the two sides of the respective cathode68 or anode 70.

The water exiting the flow conditioning elements 64, 65 is allowed toflow a fixed distance where the flow is undisturbed before the flow isdivided gently into two equal flows that enter the flow paths 72, 74 oneither side of the electrodes. This fixed distance helps the flow torecover from any disruptive effects that may have arisen from theprevious flow guides. A gentle division of the flow is achieved throughthe shape of the electrode leading edge 76, which is wedge-shaped tominimise turbulence. The fixed distance of undisturbed flow in thepreferred embodiment is around 10 mm.

It will be noted that the leading edge 76 of the anode 70 is placed at alarger distance away from the water inlet than the leading edge 76 ofthe cathode 68. The electrodialysis unit is designed such that waterflows an additional fixed distance X over the cathode before beingsubjected to electrical treatment in the reaction zone. This furtherdistance X allows any residual turbulence to dissipate and helps theflow to develop into a laminar flow before the seawater is subjected toany electrical current. This is achieved through the use of differentlengths of anode 70 and cathode 68 which permits an offset cathode/anodeconfiguration. In the preferred design shown herein this fixed distanceX is around 30 mm with a gap of 2 mm between cathode 68 and membrane.The reaction zone begins when both the anode 70 and cathode 68 arepresent in sufficient proximity, in this case this will be after thedistance X as marked on the Figure. In the reaction zone electrodialysisoccurs and as the water passes along the anode flow paths 74 and cathodeflow paths 72 in the reaction zone ion exchange occurs across themembranes 71, generating an acidic concentrate on the anode side andalkaline diluate on the cathode side as described above. The concentrateand diluate exit the electrodialysis unit via outlets 36, 38 and areused to treat water by mixing the concentrate with some or all of thediluate to provide a product of the electrodialysis unit, which isharmful to micro organisms.

On each side of the anode 70 a spacer element 78 is included in theanode flow paths 74. To avoid turbulence there are no spacer elements onthe cathode flow paths 72. In the cathode flow paths 72 conditioned flowis provided by the flow conditioning elements 64. This flow becomes morelaminar as it passes across the 10 mm region of undisturbed flow, afterwhich it is divided by the wedge shaped end 76 of the cathode 68. Thewater then flows along two cathode flow paths 72 for a further distanceof 30 mm, which acts to further promote laminar flow. By the time theincoming water enters the reaction zone in the cathode flow paths 72 theflow is generally laminar. As discussed above, this laminar flow avoidsthe build-up of brucite deposits and also helps avoid build-up of othercontaminants.

As discussed above, the preferred electrodialysis unit is made up ofseveral sets of membrane cells, with each set of cells being formed byfive anodes and six cathodes, with cathodes being placed at the outerends. With this arrangement the outer cathodes would only have oneactive side, with one flow path along the inner side of the cathodes.The outer surfaces of the outer cathodes would not be active and wouldbe blocked to prevent water flowing.

Computer modelling has been used to illustrate the advantageous effectsof the preferred embodiment.

FIGS. 10 and 11 show the effect of the two tube flow distributor system.FIG. 10 shows a plot of velocity across each of the cathode chambersalong the electrode stack in a computer model when the preferred flowdistributor 56 is not used, whereas FIG. 11 shows a plot of velocityacross each of the cathode chambers along the electrode stack in acomputer model when the preferred flow distributor 56 is used. The plotsshow flow velocity on the vertical axis with the horizontal axis showingthe distance of the cathode flow path 72 from the cathode water inlet 50at the end of the electrode stack. As can be seen by a comparison of theFigures when the flow distributor 56 is not used there is a considerablyhigher velocity in the cathode flow paths 72 at greater distances fromthe water inlet 50. When the flow distributor 56 is used the water issignificantly more evenly distributed along the length of the electrodestack.

FIGS. 12 and 13 show the effect of the flow conditioning elements 64 onwater flow across the cathode flow paths 72. FIG. 12 shows a plot ofvelocity across the width of a cathode flow path in a computer modelwhen the preferred flow conditioning elements 64 are not included, andthe water instead passes through a fan shaped region without thechannels 64 or walls 66. FIG. 13 shows a plot of velocity across thewidth of a cathode flow path in a computer model when the preferred flowconditioning elements 64 are present. The vertical axis shows flowvelocity and the horizontal axis shows the distance across the width ofa cathode flow path 72. The peaks in each plot illustrate the likelyvelocity at points across the width W of the cathode flow path 72. Thesharp troughs are due to the effect of the flow conditioning elements atthe exit of the chamber which soon dissipate away. As can be seen, whenthe average flow across the chamber is studied, the channels 64 andwalls 66 provide for a more even distribution of velocity and thus flowacross the width W of the cathode flow path 72. When they are notpresent the velocity and thus flow is less even and this would lead toturbulence and secondary flows in subsequent parts of the cathode flowpath 72.

1. An electrodialysis unit comprising: a plurality of cathodes, aplurality of anodes and a plurality of membranes; the cathodes andanodes being arranged alternately in an electrode stack, with membranesin between each cathode and anode, anode flow paths formed between themembranes and anodes and cathode flow paths formed between the membranesand cathodes; the electrodialysis unit further comprising: an inletmanifold for distributing water to the anode flow paths or to thecathode flow paths, wherein the inlet manifold comprises a first tubeprovided with holes along its length, the holes being connected to theflow paths, and a second tube located within and enclosed by the firsttube, the second tube having an inlet at one end and being closed at itssecond end and the second tube being provided with holes along itslength that open into the first tube.
 2. The electrodialysis unit asclaimed in claim 1, comprising similar inlet manifolds for both thecathode and the anode.
 3. The electrodialysis unit as claimed in claim1, wherein the inlet manifold for the cathode flow paths is arranged fora higher flow rate than the inlet manifold for the anode flow paths. 4.The electrodialysis unit as claimed in claim 2, comprising two parallelinlet manifolds for the cathode flow paths, supplying water in parallelto the cathode flow paths and a single inlet manifold for the anode flowpaths, whereby the cathode flow paths are provided with water at ahigher flow rate than the anode flow paths.
 5. The electrodialysis unitas claimed in claim 1, wherein the holes of the first tube connect tothe flow paths via flow guides.
 6. The electrodialysis unit as claimedin claim 1, wherein the holes of the first tube take the form of slitslocated transversely across the tube
 7. The electrodialysis unit asclaimed in claim 1, wherein the holes of the second tube are slitslocated transversely across the tube.
 8. The electrodialysis unit asclaimed in claim 1, wherein the second tube comprises holes on a firstside of the second tube facing the holes of the first tube and/or thesecond tube comprises holes on a second side of the second tube facingaway from the holes of the first tube.
 9. The electrodialysis unit asclaimed in claim 1, wherein the second tube is located concentricallywithin the first tube.
 10. The electrodialysis unit as claimed in claim1, wherein the anodes and cathodes are supported by separators and theseparators are provided with through holes, and wherein the inletmanifold is located along through holes in the separators with the holesin the first tube opening into flow guide features formed in theseparators.
 11. The electrodialysis unit as claimed in claim 10, whereinthe first tube is a tube formed by alignment of through holes in theseparators and second tube is a pipe inserted into the first tube. 12.The method of treating sea water comprising using the electrodialysisunit of claim
 1. 13. A method of manufacturing an electrodialysis unitcomprising: a plurality of cathodes, a plurality of anodes and aplurality of membranes; the cathodes and anodes being arrangedalternately in an electrode stack, with membranes in between eachcathode and anode, anode flow paths formed between the membranes andanodes and cathode flow paths formed between the membranes and cathodes;the method comprising: providing an inlet manifold for distributingwater to the anode flow paths or to the cathode flow paths, wherein theinlet manifold comprises a first tube provided with holes along itslength, and a second tube having an inlet at one end and being closed atits second end and the second tube also being provided with holes; themethod further comprising: providing the first tube in the electrodestack so that the holes of the first tube connect to the flow paths andlocating the second tube within the first tube so that the second tubeis within and enclosed by the first tube and the holes of the secondtube open into the first tube.
 14. The method as claimed in claim 13,wherein the anodes and cathodes are supported by separators and theseparators are provided with through holes, the method comprising:providing the inlet manifold in the electrode stack along through holesin the separators.
 15. The method as claimed in claim 14, comprisingforming the first tube by alignment of through holes in the separatorsand inserting the second tube into and along the first tube. 16-18.(canceled)
 19. The method as claimed in claim 12, wherein the sea wateris ballast water.
 20. The method as claimed in claim 13, saidelectrodialysis unit comprising: a plurality of cathodes, a plurality ofanodes and a plurality of membranes; the cathodes and anodes beingarranged alternately in an electrode stack, with membranes in betweeneach cathode and anode, anode flow paths formed between the membranesand anodes and cathode flow paths formed between the membranes andcathodes; the electrodialysis unit further comprising: an inlet manifoldfor distributing water to the anode flow paths or to the cathode flowpaths, wherein the inlet manifold comprises a first tube provided withholes along its length, the holes being connected to the flow paths, anda second tube located within and enclosed by the first tube, the secondtube having an inlet at one end and being closed at its second end andthe second tube being provided with holes along its length that openinto the first tube.